Strained molecules, electron attachment

In 1967 B. H. Mahan and C. E. Young used a new microwave method to determine the rate constant for thermal electron attachment to molecules. These quantities were determined for SF6 and C7F14 using the ECD and agreed with the values reported using the microwave method at room temperature within the experimental error [37, 38]. In addition, the temperature dependence was determined so that activation energies were obtained. This was especially important in the case of strained molecules such as cyclooctatetrene [34],... 

The facile isomerization of strained bridged molecules was inconsistent with the involvement of triadsorbed species 15. Instead, a a-alkyl adsorbed species was proposed. Its further transformation leads to a it-complex-like species (17) with a three-center, two-electron bonding with its simultaneous attachment to the surface152,157 (McKervey-Rooney-Samman mechanism) ... 

Hybridization of the carbon to which a proton is attached also influences electron density. As the proportion of s character increases from sp to sp to sp orbitals, bonding electrons move closer to carbon and away from the protons, which then become deshielded. For this reason, methane and ethane resonate at 8 0.23 and 0.86, respectively, but ethene resonates at 8 5.28. Ethyne (acetylene) is an exception in this regard, as we shall see. Hybridization contributes to shifts in strained molecules, such as cyclobutane (8 1.98) and cubane (8 4.00), for which hybridization is intermediate between sp and sp. ... 

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